CN103418388B - A kind of Fischer-Tropsch synthesis catalyst and its preparation and application - Google Patents

Abstract

A Fischer-Tropsch synthesis catalyst and its preparation and application, the catalyst contains a carrier and an active metal component selected from iron and/or cobalt loaded on the carrier, characterized in that the carrier contains P and is selected from One or more of Li, Na, Mg, K, Ca, Sr and Ba is a first auxiliary metal component modified porous heat-resistant inorganic oxide shaped product, calculated as oxide and described Based on the carrier, the content of P is 0.1-7% by weight, and the content of the first auxiliary metal component is 0.1-10% by weight. Compared with the prior art, the performance of the catalyst provided by the invention is improved.

Description

A kind of Fischer-Tropsch synthesis catalyst and its preparation and application

field of invention

The invention relates to a Fischer-Tropsch synthesis catalyst and its preparation and application.

Background technique

As global oil resources become more and more scarce and people pay more and more attention to environmental protection, people pay more and more attention to using coal and natural gas to prepare clean fuels.

Fischer-Tropsch synthesis refers to the reaction in which synthesis gas is converted into hydrocarbons on a catalyst. The products include alkanes and olefins. The products can be processed to obtain high-quality liquid fuels, such as high-quality diesel and aviation kerosene.

Commonly used Fischer-Tropsch synthesis catalysts are cobalt-based and iron-based. Compared with iron-based catalysts, cobalt-based catalysts have the advantages of long life and low water vapor shift activity. Fischer-Tropsch synthesis reactors mainly include fixed bed, slurry bed and fluidized bed. The former two are used for low-temperature Fischer-Tropsch synthesis, while the latter is used for high-temperature Fischer-Tropsch synthesis. Since Fischer-Tropsch synthesis is a strong exothermic reaction, the slurry bed with better heat transfer and online loading capacity has obvious advantages in low-temperature Fischer-Tropsch synthesis than fixed-bed reactors. However, the catalysts in the slurry bed reaction collide and rub against each other very seriously during the reaction, and fine powder is easily produced, which affects the separation of the generated wax and the catalyst, and at the same time affects the upgrading of the wax product. This requires that the slurry bed Fischer-Tropsch synthesis catalyst has good strength and wear resistance, and also has good catalytic performance.

US7402612 discloses a method for obtaining a structurally stable Fischer-Tropsch synthesis carrier by reacting boehmite with a structural stabilizer and then roasting.

CN200880012214 discloses a method for preparing a Co-based F-T synthesis catalyst using P-modified alumina as a carrier. The catalyst has the characteristics of good stability, but poor selectivity.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new catalyst with further improved performance and the preparation and application of the catalyst.

The content involved in the present invention includes:

1. A Fischer-Tropsch synthesis catalyst comprising a carrier and an active metal component selected from iron and/or cobalt loaded on the carrier, characterized in that the carrier contains P and is selected from Li, Na, Mg , K, Ca, Sr and Ba one or more of the first auxiliary metal component of the modified porous heat-resistant inorganic oxide molding, calculated as oxides and based on the carrier, so The content of P is 0.1-7% by weight, and the content of the first auxiliary metal component is 0.1-10% by weight.

2. The catalyst according to 1, characterized in that, in terms of oxides and based on the carrier, the content of P is 0.2-2.5% by weight, and the content of the first auxiliary metal component is 0.2 -5% by weight.

3. The catalyst according to 2, characterized in that, in terms of oxides and based on the carrier, the content of the P is 0.2-2% by weight, and the content of the metal component is 0.5-4% by weight .

4. The catalyst according to any one of 1, 2 or 3, characterized in that the atomic ratio of the first promoter metal component to P is 0.2-5.

5. The catalyst according to 4, characterized in that the atomic ratio of the first promoter metal component to P is 0.5-4.

6. The catalyst according to 5, characterized in that the atomic ratio of the first promoter metal component to P is 1-3.

7. The catalyst according to 1, characterized in that the porous heat-resistant inorganic oxide is selected from alumina, alumina-magnesia, silica-alumina, silica-alumina-thorium oxide, silica - One or more of alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia.

8. The catalyst according to 7, characterized in that the porous heat-resistant inorganic oxide is selected from alumina, silica-alumina and mixtures thereof.

9. The catalyst according to any one of 1, 7 or 8, characterized in that the specific surface area of the porous heat-resistant inorganic oxide is 100-250 ^m2 /g, and the pore volume is 0.3-0.8 ml/g .

10. The catalyst according to 1, characterized in that the average particle diameter of the molded product is 20-150 microns, wherein the volume fraction of particles smaller than 25 microns is not more than 5%.

11. The catalyst according to 10, characterized in that the average particle diameter of the molded product is 30-120 microns.

13. The catalyst according to 11, characterized in that the average particle diameter of the molded product is 40-100 microns.

14. The catalyst according to 1, characterized in that, based on the catalyst, the content of the metal component selected from iron and/or cobalt is 5-70% by weight.

15. The catalyst according to 14, characterized in that, based on the catalyst, the content of the metal component selected from iron and/or cobalt is 10-50% by weight.

16. The catalyst according to 15, characterized in that, based on the catalyst, the content of the metal component selected from iron and/or cobalt is 12-30% by weight.

17. The catalyst according to 1, characterized in that the catalyst contains a compound selected from La, Zr, Ce, W, Cu, Mn, Re, Ru, Rh, Pd, Os, Ir, Pt, Ag or Au One or more second promoter metal components, calculated on an elemental basis and based on the catalyst, the content of the second promoter metal components does not exceed 10% by weight.

18. The catalyst according to 17, characterized in that the content of the second promoter metal component is not more than 6% by weight on an element basis and based on the catalyst.

19. A preparation method for a Fischer-Tropsch synthesis catalyst, comprising preparing a carrier and loading an active metal component selected from iron and/or cobalt on the carrier, characterized in that, the carrier contains P and is selected from Li, Na , Mg, K, Ca, Sr and Ba one or more of the first additive metal component modified porous heat-resistant inorganic oxide molding, calculated as oxide and based on the carrier , the content of the P is 0.1-7 weight, the content of the first auxiliary metal component is 0.1-10 weight%, the preparation method of the carrier comprises:

(1) preparing an aqueous solution containing phosphate radicals and metal cations;

(2) impregnating the porous heat-resistant inorganic oxide with the solution prepared in step (1);

(3) drying and calcining the porous heat-resistant inorganic oxide impregnated in step (2).

20. The method according to 19, characterized in that, in terms of oxides and based on the carrier, the content of the P is 0.2-2.5% by weight, and the content of the first auxiliary metal component is 0.2 -5% by weight.

21. The method according to 20, characterized in that, in terms of oxides and based on the carrier, the content of the P is 0.5-2% by weight, and the content of the metal component is 0.5-4% by weight .

22. The method according to any one of 19, 20 or 21, characterized in that the atomic ratio of the first promoter metal component to P is 0.2-5.

23. The method according to 22, characterized in that the atomic ratio of the first promoter metal component to P is 0.5-4.

24. The method according to 23, characterized in that the atomic ratio of the first promoter metal component to P is 1-3.

25. The method according to 19, wherein the porous heat-resistant inorganic oxide is selected from alumina, alumina-magnesia, silica-alumina, silica-alumina-thorium oxide, silica - One or more of alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia.

26. The method according to 25, wherein the porous heat-resistant inorganic oxide is selected from alumina, silica-alumina and mixtures thereof.

27. The method according to any one of 19, 25 or 26, characterized in that the specific surface area of the porous heat-resistant inorganic oxide is 100-250 ^m2 /g, and the pore volume is 0.3-0.8 ml/g .

28. The method according to 19, characterized in that the average particle size of the molded product is 20-150 microns, wherein the volume fraction of particles smaller than 25 microns is not more than 5%.

29. The method according to 28, characterized in that the average particle size of the molded product is 30-120 microns.

30. The method according to 29, characterized in that the average particle size of the molded product is 40-100 microns.

31. The method according to 19, characterized in that, based on oxides and catalysts, the content of the metal component selected from iron and/or cobalt is 5-70% by weight.

32. The method according to 31, characterized in that, based on oxides and catalysts, the content of the metal component selected from iron and/or cobalt is 10-50% by weight.

33. The method according to 32, characterized in that, based on the oxide and based on the catalyst, the content of the metal component selected from iron and/or cobalt is 12-30% by weight.

34. The method according to 19, further comprising introducing a carrier selected from La, Zr, Ce, W, Cu, Mn, Re, Ru, Rh, Pd, Os, Ir, Pt, Ag or Au In the step of one or several second auxiliary components, the introduction amount of the second auxiliary components is not more than 25% by weight in terms of elements and based on the catalyst.

35. The catalyst according to 34, characterized in that, in terms of elements and based on the catalyst, the additive component is introduced in an amount of 0.01-10% by weight.

36. A Fischer-Tropsch synthesis method, comprising contacting a mixture of carbon monoxide and hydrogen with a catalyst under Fischer-Tropsch synthesis reaction conditions, characterized in that the catalyst is the catalyst described in any one of claims 1-18.

According to the catalyst provided by the present invention, the porous heat-resistant inorganic oxide is selected from one or several kinds of heat-resistant inorganic oxides commonly used as catalyst supports and/or substrates. For example, selected from alumina, alumina-magnesia, silica-alumina, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina One or more of aluminum-zirconia, more preferably a porous heat-resistant inorganic oxide with a specific surface area of 100-250 ^m2 /g and a pore volume of 0.3-0.8 ml/g. For example, alumina, silica-alumina and mixtures thereof with a specific surface area of 100-250 ^m2 /g and a pore volume of 0.3-0.8 ml/g. These may be commercially available or prepared by any existing method. For example, it can be prepared by calcining the precursors of porous heat-resistant inorganic oxides that are commercially available or prepared by any prior art. The calcination method and conditions are the usual calcination methods and conditions for preparing catalyst supports. For example, the calcination method is calcination under air atmosphere, wherein the calcination conditions include: the calcination temperature is 300°C-900°C, preferably 350°C-850°C, more preferably 550°C-800°C, The calcination time is 0.5 hour-12 hours, preferably 1 hour-8 hours, more preferably 2 hours-6 hours.

According to the catalyst provided by the present invention, the shaped carrier can be made into various satisfying shapes according to different requirements, such as microspheres, spheres, tablets or strips, etc. Forming can be carried out by conventional methods, for example, when the shape of the required forming carrier is microspheres that can meet the needs of the slurry bed, the porous heat-resistant inorganic oxide molding can be prepared by preparing its precursor (for example, oxidation Pseudo-boehmite, the precursor of aluminum, is prepared by spray-drying and roasting the precursor. It can also be obtained by purchasing the commercially available precursor powder of the porous heat-resistant inorganic oxide (for example, the precursor pseudo-boehmite powder obtained by spray drying) and roasting Method preparation. The calcination method and conditions are the usual calcination methods and conditions for preparing catalyst supports. For example, the calcination method is a calcination method in an air atmosphere, wherein the calcination conditions include: the calcination temperature is 300°C-900°C, preferably 350°C-850°C, more preferably 550°C-800°C , the firing time is 0.5 hours to 12 hours, preferably 1 hour to 8 hours, more preferably 2 hours to 6 hours. Generally speaking, under the premise of satisfying the requirement of slurry bed reaction, the present invention has no special limitation on the particle size of the microsphere molding. In preferred cases, the average particle size of the molding is preferably 20 microns-150 micron, wherein the volume fraction of particles smaller than 20 micron is not more than 5%, preferably the average particle diameter of the molded product is 30 micron-120 micron, more preferably 40 micron-100 micron. Wherein, the evaluation particle size of the carrier is determined by ISO 13320-1 particle size analysis-laser diffraction method.

The molded product of the modified porous heat-resistant inorganic oxide containing P and one or more first auxiliary metal components selected from Li, Na, Mg, K, Ca, Sr and Ba refers to , introducing P and one or more first auxiliary metal components selected from Li, Na, Mg, K, Ca, Sr and Ba into the formed porous heat-resistant inorganic oxide.

According to the catalyst provided by the present invention, based on the catalyst, the content of the carrier is 30-95% by weight, preferably 50-90% by weight, more preferably 70-88% by weight.

On the premise that the P and one or more first auxiliary metal components selected from Li, Na, Mg, K, Ca, Sr and Ba are introduced into the shaped carrier, the present invention specifically The loading method is not limited, and the method of impregnation is preferred. include:

(1) preparing an aqueous solution containing phosphate radicals and metal cations;

(2) impregnating the porous heat-resistant inorganic oxide with the solution prepared in step (1);

(3) drying and calcining the porous heat-resistant inorganic oxide impregnated in step (2).

Wherein, the phosphate radical in step (1) can be one or a mixture of PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- ; the metal cation is selected from Li, Na, Mg, K , Ca, Sr and Ba in one or more. They can be obtained by directly dissolving phosphates derived from said metals in water, or phosphoric acid, ammonium phosphate salts (including ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate), hydroxides, salts of said metals Separately and simultaneously soluble in water to obtain.

The drying method is a conventional method, for example, the method of heating and drying. When the drying method is heating and drying, the operating conditions of the drying include: the temperature is 80-350°C, preferably 100-300°C, and the time is 1 to 24 hours, preferably 2 to 12 hours. The calcination method and conditions are the usual calcination methods and conditions for preparing catalyst supports. For example, the calcination method is a calcination method in an air atmosphere, and the calcination conditions include: the calcination temperature is 300°C-900°C, preferably 350°C-850°C, more preferably 550°C-800°C, and the calcination The time is 0.5 hours to 12 hours, preferably 1 hour to 8 hours, more preferably 2 hours to 6 hours.

According to the catalyst provided by the present invention, wherein, the content selected from iron and/or cobalt metal components (iron or cobalt and iron and cobalt combination) is the conventional content of Fischer-Tropsch synthesis catalysts, for example, in terms of oxides and in terms of catalysts Based on , the content of the active metal component is 5-70% by weight, preferably 10-50% by weight, more preferably 12-30% by weight.

On the premise that the active metal component is sufficient to be loaded on the carrier, the present invention has no special requirements for the method of loading the active metal component selected from iron and/or cobalt on the carrier. limit. For example, the support may be contacted with a solution containing an effective amount of a compound containing an active metal component under conditions sufficient to deposit an effective amount of the active metal component on the support, such as by impregnating , co-precipitation and other methods, preferably the impregnation method, followed by drying, roasting or no roasting. The drying method is a conventional method, for example, the method of heating and drying. When the drying method is heating drying, the operating conditions of the drying include: the temperature is 80-350°C, preferably 100-300°C, and the time is 1 to 24 hours, preferably 2 to 12 hours. When the catalyst needs to be calcined, the calcining temperature is for the purpose of converting the compound containing the active metal component into its oxide, the preferred calcining temperature is 200-700°C, and the calcining time is 1-6 hours , the more preferred temperature is preferably 250-500°C, and the calcination time is 2-4 hours.

The compound containing the active metal component is preferably selected from one or more of their soluble compounds, such as one or more of water-soluble salts and complexes containing the active metal component.

The prior art shows that introducing one or more selected from La, Zr, Ce, W, Cu, Mn, Re, Ru, Rh, Pd, Os, Ir, Pt, Ag or Au into the Fischer-Tropsch synthesis catalyst The second auxiliary component is beneficial to improve the performance of the catalyst.

When the catalyst contains one or more second additive components selected from La, Zr, Ce, W, Cu, Mn, Re, Ru, Rh, Pd, Os, Ir, Pt, Ag or Au When it is used, its introduction method can be that the compound containing the auxiliary agent and the compound containing the active metal component are formulated into a mixed solution and then contacted with the carrier; it can also be that the compound containing the auxiliary agent is prepared separately. contact with the carrier, followed by drying and calcining. When the auxiliary agent and the active metal group are respectively introduced into the carrier, it is preferable to first contact the carrier with a solution containing the auxiliary agent compound, and then contact with the solution of the compound containing the active metal component after drying and roasting, for example, by ionizing Methods such as exchange, impregnation, co-precipitation, etc., preferably the impregnation method. Wherein, the concentration, dosage and impregnation of the solution make the introduction amount of the second auxiliary component in the final catalyst no more than 25% by weight, preferably 0.01-10% by weight. And satisfy, take the catalyst as the benchmark, the sum of each component is 100%.

The drying method is a conventional method, for example, the method of heating and drying. When the drying method is heating and drying, the operating conditions of the drying include: the temperature is 80-350°C, preferably 100-300°C, and the time is 1 to 24 hours, preferably 2 to 12 hours. When the catalyst needs to be roasted; the roasting method is a conventional method, wherein the operating conditions of the roasting include: the roasting temperature is 200-700°C, preferably 250-500°C, and the roasting time is 2-8 hours, preferably 3-6 hours.

According to the present invention, the catalyst is provided, and before it is used in the Fischer-Tropsch synthesis reaction, it is preferably reductively activated in the presence of hydrogen. °C to 450 °C; the reduction time is 0.5-72 hours, preferably 1-24 hours, more preferably 2-8 hours, and the reduction can be carried out in pure hydrogen or a mixture of hydrogen and inert gas , such as in a mixture of hydrogen and nitrogen and/or argon, the hydrogen pressure is 0.1-4MPa, preferably 0.1-2MPa.

According to the Fischer-Tropsch synthesis method provided by the present invention, the conditions for the contact reaction of the mixture of carbon monoxide and hydrogen with the catalyst: the preferred temperature is 160-280°C, more preferably 190-250°C, and the pressure is preferably 1-8MPa, More preferably 1-5MPa, the molar ratio of hydrogen to carbon monoxide is 0.4-2.5, preferably 1.5-2.5, more preferably 1.8-2.2, and the hourly space velocity of the gas is 200 hours ^-1 to 20000 hours ^-1 , preferably 500 hours ^-1 ~ 12000 hours ^-1 .

Compared with the prior art, the invention provides a catalyst with high wear resistance and high activity and selectivity.

Detailed ways:

The following examples will further illustrate the present invention, however, the present invention is not limited thereto.

Example 1

(1) Modified alumina and its preparation

5.87g lithium monohydrogen phosphate and 1.35g lithium hydroxide are dissolved in 147.8g water, prepare the lithium phosphate solution containing Li0.51wt% and P1.13wt% in terms of elements, then add 100g gamma-aluminum oxide 1 (Sasol product, The average particle size is 60 microns) and stirred continuously for 6h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours. A modified support having a P content of 0.88% by weight in terms of elements and a Li content of 0.39% by weight in terms of elements was prepared. Wherein the P content is measured by the XRF method, and the Li content is measured by the ICP method. The atomic ratio of Li and P is 2.0.

(2) Catalyst and its preparation

Dissolve 139g of cobalt nitrate hexahydrate in 50mL of deionized water to obtain an impregnation solution. Disperse the above-mentioned modified carrier after calcination into the above-mentioned impregnating solution, stir at room temperature for 1 hour, and then rotary evaporate to obtain a dried catalyst sample. After the sample was dried at 120°C for 2 hours, it was calcined at 375°C for 2 hours to obtain catalyst C1. The cobalt content was 20.3% by weight, and the Co content was measured by the ICP method.

(3) Catalyst application and performance

5 ml of the catalyst was weighed, and the catalyst was activated by reduction at 350° C. for 3 hours in a pure hydrogen atmosphere. Then it was transferred to an autoclave filled with 150 grams of medium wax. After the airtight inspection was completed, the temperature was raised to 110° C., and stirring was started. At the same time, synthesis gas was introduced to control the pressure at 2.5 MPa. The composition of the synthesis gas was: H ₂ : CO:N ₂ =34:17:49, continue to heat up to 220°C, and react stably at 220°C for 50h, and use online gas chromatography to analyze the tail gas composition. Define the ratio of converted CO to intake CO as CO conversion rate, the mole percentage of CO converted into methane to converted CO is methane selectivity, and the mole percentage of CO that generates C5+ hydrocarbons to converted CO is C5+ selectivity, The results are shown in Table 1.

Comparative example 1

(1) Alumina

100 g of γ-alumina 1 (Sasol product, average particle size 60 microns) was added to 150 mL of deionized water and stirred continuously for 6 h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours.

(2) Catalyst and its preparation

Dissolve 139g of cobalt nitrate hexahydrate in 50mL of deionized water to obtain an impregnation solution. Disperse the above calcined carrier into the above impregnation solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 375°C for 2 h to obtain catalyst BC1. The cobalt content in BC1 in terms of elements was 20.5% by weight, and the Co content was measured by the ICP method.

(3) Catalyst application and performance

Catalyst BC1 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Comparative example 2

(1) Modified alumina and its preparation

Dissolve 11.5g of ammonium phosphate solid in 143.5g of water to form an ammonium phosphate solution containing P1.13wt% in terms of elements, then add 100g of γ-alumina 1 (Sasol product, average particle size 60 microns) and keep stirring for 6h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours. A modified support having a P content of 0.88% by weight in terms of elements was prepared. Wherein the P content is measured by XRF method.

(2) Catalyst and its preparation

Dissolve 139g of cobalt nitrate hexahydrate in 50mL of deionized water to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 375°C for 2 h to obtain catalyst BC2. The cobalt content in elemental basis in BC2 was 20.4% by weight, and the Co content was measured by the ICP method.

(3) Catalyst application and performance

Catalyst BC2 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Comparative example 3

(1) Modified alumina and its preparation

Dissolve 7.82g of lithium nitrate in 147g of deionized water to prepare a lithium nitrate solution containing 0.51wt% Li in terms of elements, then add 100g of γ-alumina 1 (Sasol product, average particle size 60 microns) and keep stirring for 6h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours. A modified support was prepared with a Li content of 0.39% by weight in terms of elements, as measured by the ICP method.

(2) Catalyst and its preparation

Dissolve 139g of cobalt nitrate hexahydrate in 50mL of deionized water to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120 °C for 2 h, and then calcinate at 375 °C for 2 h to obtain catalyst BC3. The cobalt content in elemental basis in BC3 was 20.4% by weight, and the Co content was measured by the ICP method.

(3) Catalyst application and performance

Catalyst BC3 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Comparative example 4

(1) Modified alumina and its preparation

Add 9.9 g of ethyl orthosilicate to 150 mL of cyclohexane, and dissolve to obtain a Si solution. Add 100 g of γ-alumina 1 (Sasol product, average particle size 60 μm) into the above solution and keep stirring for 1 h. After filtering, the filter cake was dried in an oven at 180° C. for 1 hour. A modified support having an elemental Si content of 0.67% by weight was produced. Wherein the Si content is measured by XRF method.

(2) Catalyst and its preparation

Dissolve 139g of cobalt nitrate hexahydrate in 50mL of deionized water to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 375°C for 2 h to obtain catalyst BC4. The cobalt content in elemental basis in BC4 was 20.3% by weight, and the Co content was measured by the ICP method.

(3) Catalyst application and performance

Catalyst BC4 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Example 2

(1) Modified alumina and its preparation

12.88g dipotassium hydrogen phosphate and 1.02g potassium hydroxide are dissolved in 141g deionized water to prepare the potassium phosphate solution containing 3.30wt% potassium and 1.13wt% phosphorus, then add 100g gamma aluminum oxide 1 (Sasol product, average particle diameter 60 microns) and kept stirring for 6h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours. A modified support having a P content of 0.87% by weight in terms of elements and a potassium content of 2.56% by weight in terms of elements was produced. Wherein the content of P and K is measured by XRF method. The atomic ratio of K to P is 2.33.

(2) Catalyst and its preparation

Dissolve 139 g of cobalt nitrate hexahydrate and 8.30 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, and add 12.36 g of ruthenium nitrosyl nitrate solution containing 1.5% Ru to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 350°C for 2 h to obtain catalyst C2. The cobalt content in terms of elements in C2 was 20.3% by weight, the La content was 2.67% by weight, and the Ru content was 0.13% by weight, and the Co, La, and Ru contents were measured by the ICP method.

(3) Catalyst application and performance

Catalyst C2 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Example 3

(1) Modified alumina and its preparation

Dissolve 12.88g of dipotassium hydrogen phosphate in 142g of deionized water to prepare potassium phosphate solution containing 2.85wt% potassium and 1.13wt% phosphorus, then add 100g gamma-alumina 1 (Sasol product, average particle diameter 60 microns) and keep stirring 6h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours. A modified support having a P content of 0.87% by weight in terms of elements and a potassium content of 2.2% by weight in terms of elements was prepared. Wherein the content of P and K is measured by XRF method. The atomic ratio of K to P is 2.0.

(2) Catalyst and its preparation

Dissolve 139 g of cobalt nitrate hexahydrate and 8.30 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, and add 1.10 g of 1.5% Pt-containing chloroplatinic acid solution to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 375°C for 2 h to obtain catalyst C3. The cobalt content of C3 in terms of elements was 20.3% by weight, the La content was 2.67% by weight, and the Pt content was 0.011% by weight, and the Co, La, and Pt contents were measured by the ICP method.

(3) Catalyst application and performance

Catalyst C3 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Example 4

(1) Modified alumina and its preparation

Dissolve 12.88g of dipotassium hydrogen phosphate in 142g of deionized water to prepare potassium phosphate solution containing 2.85wt% potassium and 1.13wt% phosphorus, then add 100g gamma-alumina 1 (Sasol product, average particle diameter 60 microns) and keep stirring 6h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours. A modified support having a P content of 0.87% by weight in terms of elements and a potassium content of 2.2% by weight in terms of elements was prepared. Wherein the content of P and K is measured by XRF method. The atomic ratio of K to P is 2.0.

(2) Catalyst and its preparation

139 g of cobalt nitrate hexahydrate and 8.30 g of lanthanum nitrate hexahydrate were dissolved in 50 mL of deionized water, and 10.00 g of chloroplatinic acid solution containing Re2.0% was added to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 360°C for 2 h to obtain catalyst C4. The cobalt content in C4 in terms of elements was 20.3% by weight, the La content was 2.67% by weight, and the Re content was 0.14% by weight, and the Co, La, and Re contents were measured by the ICP method.

(3) Catalyst application and performance

Catalyst C4 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Example 5

(1) Modified alumina and its preparation

Dissolve 11.5g of ammonium phosphate solid in 143.5g of water to form an ammonium phosphate solution containing P1.13wt% in terms of elements, then add 100g of γ-alumina 2 (Sasol product, average particle size 55 microns) and keep stirring for 6h. After filtering, the filter cake was dried in an oven at 120°C for 6 hours, and then calcined in a muffle furnace at 800°C for 1 hour. The sample after roasting is soaked into the magnesium nitrate solution containing Mg2.6wt% that 41.7g magnesium nitrate is dissolved in 108.3g deionized water to form again, filters, and filter cake is put into 120 ℃ oven after drying for 6 hours, in the muffle furnace Baking at 800°C for 3 hours. A modified support having a P content of 0.87% by weight in terms of elements and an Mg content of 1.95% by weight in terms of elements was prepared. Wherein P and Mg contents are measured by XRF method. The atomic ratio of P to Mg is 2.90

(2) Catalyst and its preparation

Dissolve 139 g of cobalt nitrate hexahydrate and 8.30 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, and add 1.10 g of 1.5% Pt-containing chloroplatinic acid solution to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 375°C for 2 h to obtain catalyst C5. The cobalt content in C5 in terms of elements was 20.3% by weight, the La content was 2.65% by weight, and the Pt content was 0.011% by weight, and the Co, La, and Pt contents were measured by the ICP method.

(3) Catalyst application and performance

Catalyst C5 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Example 6

(1) Modified alumina and its preparation

Dissolve 2.3g of ammonium phosphate solid in 147.7g of water to form an ammonium phosphate solution containing P0.23wt% in terms of elements, then add 100g of γ-alumina 2 (Sasol product, average particle size 55 microns) and keep stirring for 6h. After filtering, the filter cake was dried in an oven at 120°C for 6 hours, and then calcined in a muffle furnace at 800°C for 1 hour. Then impregnate the calcined sample into the calcium nitrate solution containing 0.36wt% Ca formed by dissolving 3.3g of calcium nitrate in 146.7g of deionized water, filter, put the filter cake into a 120°C oven and dry it for 6 hours, then place it in a muffle furnace Baking at 800°C for 3 hours. . A modified support having a P content of 0.17% by weight on an elemental basis and a calcium content of 0.28% by weight on an elemental basis was produced. Wherein P and Ca contents are measured by XRF method. The atomic ratio of Ca to P is 1.25

(2) Catalyst and its preparation

Dissolve 139 g of cobalt nitrate hexahydrate and 8.30 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, and add 8.10 g of chloroplatinic acid solution containing Re1.5% to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 375°C for 2 h to obtain catalyst C6. The cobalt content of C6 in terms of elements was 20.3% by weight, the La content was 2.67% by weight, and the Re content was 0.09% by weight, and the Co, La, and Re contents were measured by the ICP method.

(3) Catalyst application and performance

Catalyst C6 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Example 7

(1) Modified alumina and its preparation

8.0g lithium nitrate and 22.9g ammonium nitrate were dissolved in 159g deionized water to prepare lithium phosphoric acid solution containing Li0.42wt% and P1.84wt%, then added 100g gamma-alumina 1 (Sasol product, average particle diameter 60 microns) And kept stirring for 6h. After filtering, the filter cake was dried in an oven at 140°C for 6 hours, and then baked in a muffle furnace at 800°C for 4 hours. A modified support having a P content of 1.56% by weight in terms of elements and a Li content of 0.37% by weight in terms of elements was prepared. Wherein the P content is measured by XRF method. The atomic ratio of Li to P is 1.1

(2) Catalyst and its preparation

Dissolve 139 g of cobalt nitrate hexahydrate and 8.30 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, and add 1.10 g of 1.5% Pt-containing chloroplatinic acid solution to obtain an impregnation solution. Disperse the calcined modified carrier into the impregnating solution and stir at room temperature for 1 h, then rotary evaporate to obtain a dried catalyst sample, dry the sample at 120°C for 2 h, and then calcinate at 375°C for 2 h to obtain catalyst C7. The cobalt content of C7 in terms of elements was 20.3% by weight, the La content was 2.63% by weight, and the Pt content was 0.012% by weight, and the Co, La, and Pt contents were measured by the ICP method.

(3) Catalyst application and performance

Catalyst C7 was evaluated according to the same method and conditions as in Example 1, and the results are shown in Table 1.

Table 1

*Abrasion rate is the mass fraction of catalyst fine powder (<5 μm) after reaction.

The results in Table 1 show that the comprehensive performance of the catalyst provided by the present invention (including: methane selectivity, C ₅ + selectivity and wear resistance) is better than that of the catalyst provided by the prior art.

Claims (33)

1. a fischer-tropsch synthetic catalyst, containing carrier and load chosen from Fe on this carrier and/or the active metal component of cobalt, it is characterized in that, described carrier is the article shaped of the porous heat-resistant inorganic oxide containing P and be selected from the first promoter metal component modification of one or more in Li, Na, Mg, K, Ca, Sr and Ba, with oxide basis and with described carrier for benchmark, the content of described P is 0.1-7 % by weight, the content of described first promoter metal component is 0.1-10 % by weight, and the atomic ratio of described first promoter metal component and P is 0.2-5.

2. catalyst according to claim 1, is characterized in that, with oxide basis and with described carrier for benchmark, the content of described P is 0.2-2.5 % by weight, and the content of described first promoter metal component is 0.2-5 % by weight.

3. catalyst according to claim 2, is characterized in that, with oxide basis and with described carrier for benchmark, the content of described P is 0.5-2 % by weight, and the content of described metal component is 0.5-4 % by weight.

4. the catalyst according to any one of claim 1,2 or 3, is characterized in that, the atomic ratio of described first promoter metal component and P is 0.5-4.

5. catalyst according to claim 4, is characterized in that, the atomic ratio of described first promoter metal component and P is 1-3.

6. catalyst according to claim 1, it is characterized in that, described porous heat-resistant inorganic oxide is selected from one or more in aluminium oxide, alumina-silica magnesium, silica-alumina, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia.

7. catalyst according to claim 6, is characterized in that, described porous heat-resistant inorganic oxide is selected from aluminium oxide, silica-alumina and composition thereof.

8. the catalyst according to claim 1,6 or 7 any one, is characterized in that, the specific area of described porous heat-resistant inorganic oxide is 100-250 rice ²/ gram, pore volume is 0.3-0.8 ml/g.

9. catalyst according to claim 1, is characterized in that, the average grain diameter of described article shaped is 20-150 micron, wherein, is less than the grain volume fraction of 25 microns for being not more than 5%.

10. catalyst according to claim 9, is characterized in that, the average grain diameter of described article shaped is 30-120 micron.

11. catalyst according to claim 10, is characterized in that, the average grain diameter of described article shaped is 40-100 micron.

12. catalyst according to claim 1, is characterized in that, are benchmark with oxide basis and with catalyst, and the content of described chosen from Fe and/or cobalt metal component is 5 ~ 70 % by weight.

13. catalyst according to claim 12, is characterized in that, are benchmark with oxide basis and with catalyst, and the content of described chosen from Fe and/or cobalt metal component is 10 ~ 50 % by weight.

14. catalyst according to claim 13, is characterized in that, are benchmark with oxide basis and with catalyst, and the content of described chosen from Fe and/or cobalt metal component is 12 ~ 30 % by weight.

15. catalyst according to claim 1, it is characterized in that, containing one or more the second promoter metal components be selected from La, Zr, Ce, W, Cu, Mn, Re, Ru, Rh, Pd, Os, Ir, Pt, Ag or Au in described catalyst, in element and with described catalyst for benchmark, the content of described second promoter metal component is no more than 10 % by weight.

16. catalyst according to claim 15, is characterized in that, in element and with described catalyst for benchmark, the content of described second promoter metal component is no more than 6 % by weight.

The preparation method of 17. 1 kinds of fischer-tropsch synthetic catalysts, comprise the active metal component preparing carrier load chosen from Fe and/or cobalt on this carrier, it is characterized in that, described carrier is for containing P and being selected from Li, Na, Mg, K, Ca, the article shaped of the porous heat-resistant inorganic oxide of the first promoter metal component modification of one or more in Sr and Ba, with oxide basis and with described carrier for benchmark, the content of described P is 0.1-7 % by weight, the content of described first promoter metal component is 0.1-10.0 % by weight, the atomic ratio of described first promoter metal component and P is 0.2-5, the preparation method of described carrier comprises:

(1) preparation contains the aqueous solution of phosphate radical and metal cation;

(2) with solution impregnation porous heat-resistant inorganic oxide prepared by step (1);

(3) the dry also roasting of the porous heat-resistant inorganic oxide that will flood through step (2).

18. methods according to claim 17, is characterized in that, with oxide basis and with described carrier for benchmark, the content of described P is 0.2-2.5 % by weight, and the content of described first promoter metal component is 0.2-5 % by weight.

19. methods according to claim 18, is characterized in that, with oxide basis and with described carrier for benchmark, the content of described P is 0.5-2.0 % by weight, and the content of described metal component is 0.5-4 % by weight.

20. methods according to claim 17,18 or 19 any one, it is characterized in that, the atomic ratio of described first promoter metal component and P is 0.5-4.

21. methods according to claim 20, is characterized in that, the atomic ratio of described first promoter metal component and P is 1-3.

22. methods according to claim 17, it is characterized in that, described porous heat-resistant inorganic oxide is selected from one or more in aluminium oxide, alumina-silica magnesium, silica-alumina, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia.

23. methods according to claim 22, is characterized in that, described porous heat-resistant inorganic oxide is selected from aluminium oxide, silica-alumina and composition thereof.

24. methods according to claim 17,22 or 23 any one, it is characterized in that, the specific area of described porous heat-resistant inorganic oxide is 100-250 rice ²/ gram, pore volume is 0.3-0.8 ml/g.

25. methods according to claim 17, is characterized in that, the average grain diameter of described article shaped is 20-150 micron, wherein, are less than the grain volume fraction of 25 microns for being not more than 5%.

26. methods according to claim 25, is characterized in that, the average grain diameter of described article shaped is 30-120 micron.

27. methods according to claim 26, is characterized in that, the average grain diameter of described article shaped is 40-100 micron.

28. methods according to claim 17, is characterized in that, are benchmark with oxide basis and with catalyst, and the content of described chosen from Fe and/or cobalt metal component is 5 ~ 70 % by weight.

29. methods according to claim 28, is characterized in that, are benchmark with oxide basis and with catalyst, and the content of described chosen from Fe and/or cobalt metal component is 10 ~ 50 % by weight.

30. methods according to claim 29, is characterized in that, are benchmark with oxide basis and with catalyst, and the content of described chosen from Fe and/or cobalt metal component is 12 ~ 30 % by weight.

31. methods according to claim 17, it is characterized in that, also comprise the step introducing one or more the second adjuvant components be selected from La, Zr, Ce, W, Cu, Mn, Re, Ru, Rh, Pd, Os, Ir, Pt, Ag or Au in carrier, be benchmark in element and with catalyst, the introduction volume of described second adjuvant component is no more than 25 % by weight.

32. methods according to claim 31, is characterized in that, are benchmark in element and with catalyst, and the introduction volume of described second adjuvant component is 0.01-15 % by weight.

33. 1 kinds of Fischer-Tropsch synthesis methods, be included under Fischer-Tropsch synthesis condition and the mixture of carbon monoxide and hydrogen and catalyst exposure reacted, it is characterized in that, described catalyst is the catalyst described in aforementioned any one of claim 1-16.